DK2133319T3 - A method for producing lower kulstofolefiner from methanol and / or dimethyl ether - Google Patents
A method for producing lower kulstofolefiner from methanol and / or dimethyl ether Download PDFInfo
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- DK2133319T3 DK2133319T3 DK07785182.2T DK07785182T DK2133319T3 DK 2133319 T3 DK2133319 T3 DK 2133319T3 DK 07785182 T DK07785182 T DK 07785182T DK 2133319 T3 DK2133319 T3 DK 2133319T3
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- methanol
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- dimethyl ether
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims description 293
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 title claims description 114
- 238000004519 manufacturing process Methods 0.000 title description 7
- 238000006243 chemical reaction Methods 0.000 claims description 192
- 239000003054 catalyst Substances 0.000 claims description 89
- 238000000034 method Methods 0.000 claims description 67
- 150000001336 alkenes Chemical class 0.000 claims description 61
- 238000000926 separation method Methods 0.000 claims description 61
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 56
- 239000005977 Ethylene Substances 0.000 claims description 56
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 54
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 54
- 239000000047 product Substances 0.000 claims description 48
- 125000004432 carbon atom Chemical group C* 0.000 claims description 26
- 239000002808 molecular sieve Substances 0.000 claims description 25
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 25
- 229930195733 hydrocarbon Natural products 0.000 claims description 19
- 150000002430 hydrocarbons Chemical class 0.000 claims description 19
- 230000008569 process Effects 0.000 claims description 18
- -1 ethylene, propylene Chemical group 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 10
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 10
- 229910021536 Zeolite Inorganic materials 0.000 claims description 9
- 239000010457 zeolite Substances 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000011148 porous material Substances 0.000 claims description 8
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims description 8
- 230000002378 acidificating effect Effects 0.000 claims description 6
- 238000009826 distribution Methods 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 239000004927 clay Substances 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 229910052570 clay Inorganic materials 0.000 claims description 2
- 239000012467 final product Substances 0.000 claims description 2
- 239000011159 matrix material Substances 0.000 claims description 2
- 239000003377 acid catalyst Substances 0.000 claims 2
- 239000007787 solid Substances 0.000 claims 1
- 239000000203 mixture Substances 0.000 description 22
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 18
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 13
- 239000004215 Carbon black (E152) Substances 0.000 description 12
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 10
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 9
- 239000001294 propane Substances 0.000 description 9
- 238000011069 regeneration method Methods 0.000 description 7
- 238000005336 cracking Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 230000008929 regeneration Effects 0.000 description 6
- 230000009466 transformation Effects 0.000 description 6
- 230000029936 alkylation Effects 0.000 description 5
- 238000005804 alkylation reaction Methods 0.000 description 5
- 150000001491 aromatic compounds Chemical class 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 230000001131 transforming effect Effects 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 238000004817 gas chromatography Methods 0.000 description 4
- 239000004005 microsphere Substances 0.000 description 4
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 3
- 238000004939 coking Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- HNRMPXKDFBEGFZ-UHFFFAOYSA-N 2,2-dimethylbutane Chemical compound CCC(C)(C)C HNRMPXKDFBEGFZ-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000002168 alkylating agent Substances 0.000 description 2
- 229940100198 alkylating agent Drugs 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 238000007069 methylation reaction Methods 0.000 description 2
- 230000037361 pathway Effects 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- LJPCNSSTRWGCMZ-UHFFFAOYSA-N 3-methyloxolane Chemical compound CC1CCOC1 LJPCNSSTRWGCMZ-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000006757 chemical reactions by type Methods 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229940050176 methyl chloride Drugs 0.000 description 1
- 230000011987 methylation Effects 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000011369 resultant mixture Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- IAQRGUVFOMOMEM-ONEGZZNKSA-N trans-but-2-ene Chemical compound C\C=C\C IAQRGUVFOMOMEM-ONEGZZNKSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C11/00—Aliphatic unsaturated hydrocarbons
- C07C11/02—Alkenes
- C07C11/06—Propene
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/40—Ethylene production
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
DESCRIPTION
Field of the invention [0001] The present invention relates to a method for converting methanol or/and dimethyl ether into light olefins.
Background of the invention [0002] Light olefins such as ethylene, propylene are the basic raw material for chemical industry. Conventionally, ethylene and propylene mainly come from steam cracking of hydrocarbon feedstock such as naphtha, light diesel oil, hydrogenation cracking tail oil. Recently, as the price of crude oil has been dramatically rising up, the cost for producing ethylene and propylene from the above feedstock has been increasing. Also, in the conventional processes for producing ethylene and propylene, high temperature tubular furnace cracking technologies with a high energy consumption are generally used. All these factors urge the development of new olefin production technologies. Novel technical pathways of preparation of lower olefins from non-petroleum materials have caught much attention in the past years. Among those, the one, characterized in that coal or natural gas is transformed into methanol through syngas, and then methanol is transformed into lower olefins, has been of extensive interest. The process of selectively producing light olefins from methanol (or dimethyl ether generated from the dehydration of methanol) in the presence of molecular sieve catalysts is referred to as MTO process. The methods and technologies for transforming methanol into light olefins are closely correlated to the catalysts used therein. It is well known that two classes of catalysts are used in these processes. One class is the catalysts based on ZSM-5 molecular sieves with medium size micropores, characterized by higher yield of propylene and lower yield of ethylene in the distribution of the products, slightly lower total yield of ethylene and propylene, strong anti-coking ability of the catalysts and longer operating cycle. The reaction techniques suitable for the above class are usually fixed bed reaction techniques with periodical switches between reactions and switches between reactions and regenerations. Another class of catalysts is based on the molecular sieves with smaller pore size, characterized by high total yield of ethylene and propylene as well as higher yield of ethylene in the product. Because this class of catalysts has a higher coking rate, the processes generally utilize fluidized bed techniques with continuous reaction-regeneration of the catalysts.
[0003] US patent US6613951 B1 and Chinese patent CN1352627A disclose methods for converting methanol or/and dimethyl ether into C2-C4 olefins, wherein the feed are contacted with a catalyst containing a 10-ring zeolite under 370-480°C with a methanol partial pressure of 2,07 x 105 Pa (30psia) to 1,03 x 106 Pa (150 psia).
[0004] Chinese patent CN1302283A discloses a method for converting methanol or/and dimethyl ether into C2-C4 olefins and aromatics higher than C9, wherein a portion of the aromatics is returned back to the reactor and co-fed with methanol or dimethyl ether under 350-480°C to increase the yield of olefins. US patent US6506954 B1 discloses a method for converting methanol or/and dimethyl ether into C2-C4 olefins, wherein aromatic compounds are added to increase the yield of olefin. The catalysts used in the method are porous crystalline materials with a pore size larger than the dynamic diameter of aromatic compounds. Reactions are conducted at 350-480°C. The partial pressure for methanol is not lower than 10 psia. The 2,2-dimethyl butane diffusion coefficient of the catalysts is 0.1-20 sec"1(120°C, 60 torr). US patent US6538167 B1 discloses a similar method, suggesting that the reaction conditions shall ensure the alkylation of aromatic compounds.
[0005] US patent US6710218 B1 discloses a method for converting methanol into lower olefins, utilizing SAPO-34 as the catalyst. A fluidized bed reactor-regenerator process is used. The selectivity of lower olefins is higher than 90 wt %, in which more than 80 wt % is ethylene and propylene. The ethylene/propylene ratio ranges from 0.69 to 1.36 by the modification of the reaction temperature and space velocity of feed.
[0006] US patents US6437208 B1 and US6740790 B2 disclose a method for making olefins from oxygenate-containing feedstock by employing a fluidized bed reaction technique in the presence of a silicoalumophosphate molecular sieve catalyst. The conversion conditions include that the silicon/aluminum ratio in the catalyst is lower than 0.65; the average catalyst feedstock exposure index (ACFE) is at least 1; and the reaction temperature is 200-700°C.
[0007] US patent US6455747 B1 discloses a method for converting oxygenate-containing feed into olefins. The reaction conditions include that the superficial velocity is not lower than 2 m/s and WHSV is 1-5000 hr'1. Similar methods are disclosed in US patents US6552240 B1 and US6717023 B2.
[0008] Chinese patent CN1163458C discloses a MTO reaction process using SAPO-34 catalyst and a dense phase fluidized bed. The conversion of methanol is 93-100%. The total selectivity for ethylene and propylene is higher than 80% by weight. The ethylene/propylene ratio of the product may be changed by altering the conditions such as reaction temperature, feeding space velocity.
[0009] US patent US6613950 B1 discloses a method for producing olefin from oxygenate-containing feedstock. A silicoalumophosphate molecular sieve is utilized as the catalyst. Following gas stripping, a portion of the exposed catalyst is returned back to the reaction zone without regeneration to be contacted with the feedstock.
[0010] US patent US6743747 B1 discloses a method for converting oxygenate feedstock into olefins with a silicoalumophosphate molecular sieve as the catalyst. Aromatic compounds are added to the feed proportionally, so that the yield of olefins, in particular ethylene, is enhanced.
[0011] US patent US6051746 A1 discloses a method for converting oxygenate organic material into olefins with small pore molecular sieve catalysts. The catalyst is pre-treated with the aromatic compounds containing nitrogen and at least 3 interconnected rings, in order to decrease the amount of byproducts such as ethane and increase the yield of olefins.
[0012] US patent US6518475 B2 discloses a method for converting oxygenates into lower olefins. The catalyst utilized is a silicoalumophosphate molecular sieve. In order to obtain a higher yield of ethylene, acetone is added to the feed, or the catalyst is pre-treated with acetone.
[0013] US patents US20050215840 A1 and US6965057 B2 discloses a method for converting oxygenate feedstock, including methanol, into lower olefins. A riser technique is used. At least a portion of the catalyst deactivated by coking enters the regenerator to burn off the carbonaceous deposit. At least 60% of the molecular oxygen carried by catalyst is then removed by gas stripping. The catalyst is returned back into the reactor to be re-contacted with the feedstock.
[0014] US patent US6673978 B2 discloses a method for converting oxygenate feedstock into olefins. A silicoalumophosphate molecular sieve is used as the catalyst. The fluidized bed reaction device employed includes at least one reaction zone and one circulation zone. A temperature of 250°C or higher is set up for the circulation zone, and specified portions of the catalyst circulates between the reaction zone and circulation zone.
[0015] Chinese patent CN1356299A discloses a technique utilizing SAPO-34 catalyst and a parallel-flow descending type fluidized bed. With this method, the byproduct such as alkanes in the MTO procedure is decreased, thus the difficulty of the subsequent separation is lowered. The conversion of methanol is higher than 98%, and the selectivity of olefins is higher than 90 wt %.
[0016] Chinese patent CN1190395C discloses a method for producing lower olefins from oxygenate compounds, such as methanol or dimethyl ether, comprising the step of feeding at several locations along the axis direction of the catalyst bed, wfnich improves the selectivity of ethylene.
[0017] Chinese patent CN1197835C provides a method for transforming oxygenate compounds into olefins. A main olefin product yield of 45 wt % could be achieved under the conditions that the feeding is carried out while the oxygenate proportion index is at least 0.5; and the partial pressure-rate compensation factor is kept at least 1,45 x 10"® Pa"1 hr"1 (0.1 psia'1 hr"1).
[0018] With the technologies and methods disclosed above, the distributions of products are relatively fixed. Although the composition of products could be modulated by altering the reaction conditions in some of these patented methods, the extent of the modulation is much limited. The changing demand for olefins in the global market, particularly the rapidly increasing demand for propylene in the recent years, requires a more flexible distribution of the olefin products transformed from methanol, especially in the ratio of ethylene to propylene, i.e. the two main olefin products. In view of above, several patents have disclosed the methods for changing the distribution of products by recycling a portion of the products. US patent US6441262 B1 and Chinese patent CN1489563A disclose methods for transforming oxygenate feedstock into lower olefins, wherein methanol, ethanol, 1-propanol, 1-butanol or mixture thereof is contacted with the catalyst to generate olefins, and then the catalyst is contacted with said oxygenate compounds to generate olefins, so that the ratio of products, including ethylene, propylene and butylene, could be changed without shutdown.
Canadian patent CA2408590 discloses a technique for transforming methanol into propylene. Reactors connected in series are utilized to produce propylene, dimethyl ether and higher hydrocarbon, and the resultant dimethyl ether and a portion of the higher hydrocarbons are returned back into the reactors connected in series and subjected to a further reaction, in order to increase the yield of propylene. US patents US5914438 and US6303839 B1 disclose methods for producing lower olefins, including that oxygenate feedstock are contacted with the catalyst containing aluminophosphate and transformed into C2-C4 olefin, and partial C3 and C4 fraction are recycled and cracked to increase the yield of ethylene and propylene. The recycling reaction could be carried out in the riser of the fluidized bed or in a separate reaction zone.
[0019] US patent US5990369 disclosed a method for producing lower olefins, including that oxygenate feedstock are contacted with a catalyst containing aluminophosphate and transformed into C2-C4 olefins, and a portion of the olefin products are recycled and cracked to increase the yield of ethylene, propylene and butylenes, wherein either propylene could be recycled to increase production of ethylene, or the ethylene and butylenes could be recycled to increase production of propylene.
[0020] The present invention is based on the theory that during the transformation from methanol to olefins, there exist several reaction trends: Certain reaction trends can be enforced by employing different reaction conditions in different reaction zones, so that the composition of the products can be changed. The commonly well known transformation route from methanol to hydrocarbons under acidic catalysts is shown as follows:
[0021] It is a complicated reaction network, roughly including two reaction directions: one is the reactions involving the increase of the number of carbon atoms- light olefins such as ethylene, propylene forms higher hydrocarbon molecules through reactions such as oligomerization ; the other one is the reactions involving the reduce of number of carbon atoms- higher hydrocarbon molecules are cracked into light olefin such as ethylene and propylene. In order to obtain lower olefins such as ethylene and propylene, certain reaction conditions such as higher reaction temperature which favors the transformation towards the cracking of higher hydrocarbon are usually required. Another pathway is to utilize the shape selectivity of molecular sieve catalysts to ensure that the reactions occur in the channels so that only the smaller hydrocarbon molecules may diffuse out and lower olefins are formed at a high selectivity. Recently, it has been found in some studies that the reaction types involved in the MTO transformation procedure are more complicated than the above scheme. For instance, Svelle et al has discovered in an isotope research (Kinetic studies of zeolite-catalyzed methylation reactions. J. Catal., 224 (1), 115-123, 2004) that during the transformation from methanol to olefin, alkylation occurs between olefins and methanol, so that the number of carbon atoms in olefin is increased: CH3OH + CnH2n = Cn+1 H2n+2+H20 [0022] In particular, the alkylation between one molecule of ethylene and one molecule of methanol forms one molecule of propylene.
[0023] US patent US3906054 discloses a technology for alkylation of olefins, comprising that olefins are contacted with catalysts, i.e. a zeolite with silica to alumina ratio of 12 or higher, in the presence of alkylating agents. P modification is used, wherein the minimum P content is 0.78 wt %. The olefins that may be alkylated include ethylene, propylene, butylene-2 and isobutylene, and the suitable alkylating agents are methanol, dimethyl ether and methyl chloride.
[0024] The international patent W02005/056504 A1 discloses a method for efficiently preparing propylene from ethylene and methanol or/and dimethyl ether, including that ethylene and methanol or/and dimethyl ether react in the presence of catalysts to generate propylene. It is characterized in that the amount of ethylene flowing out of the reaction system is reduced as compared with the amount of ethylene added to the reaction system. The yield of propylene reaches 40 mol % based on the moles of methanol or two times of the moles of dimethyl ether which is added to the reaction system.
Disclosure of the invention [0025] In the first aspect of the present invention, there is provided a method as defined by claim 1.
[0026] The present invention provides a method for converting methanol or/and dimethyl ether into light olefins, whereby the selectivity of lower olefins is improved in the whole process and the ratio of ethylene/propylene of the product is modulated, comprising feeding methanol or/and dimethyl ether at three reaction zones and strengthening the following two reaction trends, wherein one is to strengthen the cracking of higher olefins to increase the total yield of ethylene and propylene; and the other is to strengthen the alkylation of ethylene and methanol or/and dimethyl ether to co-transform a portion of ethylene and methanol or/and dimethyl ether into propylene.
[0027] The present invention provides a method for transforming methanol or/and dimethyl ether into light olefins, characterized in that at least 3 independent reaction zones and at least one separation zone are employed. The feedstock of methanol or/and dimethyl ether is divided into 3 streams. The first stream enters the first reaction zone, being contacted with a molecular sieve catalyst and transformed into a mixture of ethylene, propylene, butylenes and higher hydrocarbons. The catalyst used in such reaction zone can be a silica-alumina zeolite or/and a silicophosphate molecular sieve, with a pore size of 0.3-0.6 nm, such as ZSM-5, ZSM-11, SAPO-34, SAPO-11. The contact of the feedstock (i.e. methanol or/and dimethyl ether) with the catalyst is performed in reactors such as fixed beds, fluidized beds or risers. In the case of fixed bed reactors, a series of reactors in this reaction zone are set for alternative switches to regeneration state. In the case of fluidized bed and riser reactors, the devices for continuous catalyst regeneration are included. The reaction conditions should ensure a conversion of methanol or/and dimethyl ether higher than 99%, a sufficiently high yield of ethylene and propylene, and an as low as possible yield of low-value products such as methane and coke. The suitable reaction temperature in said reaction zone is 350-700°C.
[0028] The stream flowing out of the reaction zone described above enters into said separation zone to undergo a preliminary separation. The streams flowing out of the other two reaction zones enter into said separation zone as well. Three effluent streams are formed from said separation zone, including a stream containing ethylene, ethane, and lighter fractions; a stream containing propylene and propane; and a stream containing C4 and heavier fractions. Among them, the stream containing propylene and propane fractions undergoes a further separation to remove propane and form a propylene product. At least a portion of the stream containing ethylene, ethane and lighter products enters the second reaction zone, and the rest are led to a further separation to remove other fractions to form ethylene product. At least a portion of the stream containing C4 and heavier fractions enters the third reaction zone, and the rest part forms a mixed hydrocarbon product with carbon atoms of 4 and more, or forms C4 product, C5 product by further separation.
[0029] The second stream of methanol or/and dimethyl ether enters the second reaction zone. At the same time, at least a portion of said stream containing ethylene, ethane and lighter products which comprise C2H4, C2f%, CH4, H2 and ΟΟχ[χ=1 or 2),coming from the separation zone, enters into the same reaction zone. After sufficiently mixed, these two streams are contacted with a molecular sieve catalyst, so that a mixed stream containing propylene are generated and in turn fed into the separation zone. The catalysts used in this reaction zone can be a silica-alumina zeolite, a silicophosphate molecular sieve, vwth a pore size of 0.3-0.6 nm, such as ZSM-5, ZSM-11, SAPO-34, SAPO-11. The reaction conditions should ensure that the conversion of methanol or/and dimethyl ether is greater than 99% and that the propylene is generated at high selectivity. The suitable reaction temperature in such reaction zone is 250-600°C. The contact between the feedstock mixture and the catalyst can be performed in various kinds of reactors including fixed beds, fluidized beds and risers. In the case of fixed bed reactors, a series of reactors are included in this reaction zone for alternative switches to regeneration state. In the case of fluidized bed and riser reactors, the devices for continuous regeneration catalysts are included.
[0030] The third stream of methanol or/and dimethyl ether enters the third reaction zone. At the same time, at least a portion of the stream containing C4 and heavier fractions, coming from the separation zone, enters into the same reaction zone. This stream containing C4 and heavier fractions are contacted with a catalyst in the third reaction zone and cracked to form a mixed product comprising ethylene and propylene. The cracking reaction is endothermic, and the reaction heat is at least partially provided by the transformation of the feedstock of methanol or/and dimethyl ether which is introduced into said reaction zone, in the presence of a catalyst. Methanol or/and dimethyl ether contacts the catalyst either together with said stream containing C4 and heavier fractions, or at different sections in the same reaction zone and indirectly provide the heat for the cracking reaction of the latter. Meanwhile, the contacting of methanol or/and dimethyl ether with the catalyst generates products including ethylene, propylene and C4 and heavier fractions. The catalysts used in such reaction zone can be a silica-alumina zeolite or a silicophosphate molecular sieve, with a pore size of 0.3-0.6 nm, such as ZSM-5, ZSM-11, SAPO-34, SAPO-11. The reaction conditions should ensure that the conversion of methanol or/and dimethyl ether is greater than 99% and that the ethylene and propylene are generated at high selectivity. The suitable reaction temperature in said reaction zone is 450-700°C. The contact between the material streams and the catalyst can be done in all kinds of reactors including fixed beds, fluidized beds and risers. The stream flowing out of the reactor contains ethylene, propylene and C4 and heavier fractions and enters into the separation zone described above.
[0031] In the above method, a portion of the stream containing ethylene, ethane and lighter products, coming from said separation zone, enters the second reaction zone, and a portion of the stream containing C4 and heavier fractions, coming from said separation zone, enters the third reaction zone, at certain proportions, respectively. These two proportions change from 1% to 99% by weight. The stream of methanol or/and dimethyl ether that enters into the second reaction zone accounts for 1-30 % of the total stream of methanol or/and dimethyl ether by weight. The stream of methanol or/and dimethyl ether that enters into the third reaction zone accounts for 1-40 % of the total stream of methanol or/and dimethyl ether by weight. In the distribution of the final olefin products, the ethylene/propylene ratio is 0-2.0 (by weight).
[0032] Based on the above disclosure of the invention, the present invention can be summarized as follow.
[0033] The present invention provides a method for converting methanol or/and dimethyl ether into light olefins, characterized in that at least three independent reaction zones and at least one separation zone are employed, and that all feedstock of methanol or/and dimethyl ether are divided into three parts and fed at said independent reaction zones, and that the ratio of different types of olefins in the final product can be modulated by changing the feeding ratio for each reaction zone, the method comprising the steps of: (a) converting methanol or/and dimethyl ether into a mixed hydrocarbon stream that contains ethylene, propylene and olefin with 4 and more carbon atoms in the presence of acidic catalysts in the first reaction zone, and leading said hydrocarbon stream into said separation zone; (b) carrying out the separation of all the effluent streams of said three reaction zones in said separation zone to form a C3 fraction which flows out of said separation zone to form a propylene product by further separation, a fraction with no more than 2 carbon atoms and a fraction with 4 or more carbon atoms, at least a portion of said effluent stream with no more than 2 carbon atoms being led into the second reaction zone with the rest being further separated to obtain ethylene product, at least a portion of said effluent stream with 4 or more carbon atoms being led into the third reaction zone with the rest being further separated to obtain butylene product; (c) contacting the methanol or/and dimethyl ether together with at least a portion of effluent stream coming from said separation zone and containing no more than 2 carbon atoms with an acidic catalyst in the second reaction zone and leading the formed mixture containing propylene into said separation zone; (d) contacting methanol or/and dimethyl ether as well as at least a portion of said effluent stream coming from said separation zone and containing 4 or more carbon atoms with an acidic catalyst in the third reaction zone, and leading the resultant mixture containing certain concentration of ethylene and propylene into said separation zone.
[0034] According to the above method, the stream of methanol or/and dimethyl ether that enter(s) the second reaction zone accounts for 1-30 wt % of the total stream of methanol or/and dimethyl ether. The stream of methanol or/and dimethyl ether that enter(s) the third reaction zone accounts for 1-40 wt % of the total stream of methanol or/and dimethyl ether. 1-99 wt% of the stream flowing out of the separation zone and containing 2 or fewer carbon atoms enters the second reaction zone. 1-99 wt% of the stream flowing out of the separation zone and containing 4 or fewer carbon atoms enters the third reaction zone.
[0035] According to the above method, the catalysts used in each reaction zone may include a silica-alumina zeolite or/and a silicophosphate molecular sieve, and their derivatives obtained by elemental modification. The pore sizes for the silica-alumina zeolite or/and silicophosphate molecular sieve are 0.3-0.6 nm. The catalysts include matrix materials comprising one or more of silica, alumina or clay.
[0036] According to the method of the present invention, the reaction temperature in the first reaction zone is 350-700°C; the reaction temperature in the second reaction zone is 250-600°C; and the reaction temperature in the third reaction zone is 450-700°C.
[0037] According to the method of the present invention, fluidized beds, fixed beds or moving bed reactors can be utilized in the first, second and third reaction zone, respectively.
Brief Description of the Drawing [0038] Figure 1 is the schematic flow chart of the method according to the present invention. As shown in figure 1, all the feedstock of methanol or/and dimethyl ether is divided into 3 streams. The stream 8 of methanol of/and dimethyl ether enters into the reaction zone 1, and is transformed into a mixed stream 11 containing ethylene, propylene, butylenes and hydrocarbon with more carbon atoms. The mixed stream 11 then enters into the separation zone 4 and undergoes a preliminary separation. The stream 12 flowing out of the reaction zone 2 and the stream 13 flowing out of the reaction zone 3 enter into the separation zone 4 as well. Three effluent streams are formed from the separation zone 4, including the stream containing ethylene, ethane and lighter fractions; the stream containing propylene and propane; and the stream containing C4 and heavier fractions. Among them, the stream 16 containing propylene and propane undergoes a separation step in the separation zone 5, so that propane is removed and the propylene product 19 is generated. At least a portion of the stream containing ethylene, ethane and lighter products (stream 14) enters into the reaction zone 2, with the rest (stream 17) entering into the separation zone 6 and going through a separation step to remove fractions other than ethylene to form the ethylene product 20. At least a portion of the stream containing C4 and heavier fractions (stream 15) enters into the reaction zone 3, with the rest forming a mixed hydrocarbon product with 4 or more carbon atoms (stream 18) or undergoing a separation step in the separation zone 7 to form products as C4 product (stream 21) and products with 5 or more carbon atoms. The stream 9 of methanol or/and dimethyl ether enters into the reaction zone 2. At the same time, the stream 14 flowing out of the separation zone 4 and containing ethylene, ethane and lighter products enters into the same reaction zone, and the stream 12 flowing out of the reaction zone 2 and containing propylene enters into the separation zone 4. The stream 10 of methanol or/and dimethyl ether enters into the reaction zone 3. At the same time, a portion of stream flowing out of separation zone 4 and containing C4 and heavier fractions (stream 15) enters into the same reaction zone, and the stream 13 flowing out of the reaction zone 3 and containing ethylene, propylene and hydrocarbons with 4 and more carbon atoms enters into the separation zone 4.
Embodiments of the invention [0039] The present invention will now be further illustrated in details by the following Examples.
Example 1*: The conversion of methanol over a molecular sieve catalyst.
[0040] Catalyst A was prepared as follows: after mixed with silicasol (Zhejiang Yuda Chemical Industry CO., Ltd.) completely, a ZSM-5 molecular sieve (The Catalyst Plant of Nankai University, with silicon/aluminum ratio of 50) was shaped by mixing, kneading and extruding; air dried at room temperature; and further baked at 550°C for 4 hours. The above samples were immersed in a lanthanum nitrate solution of a certain concentration, and baked to dryness. Then, the resultant material was immersed in a phosphoric acid solution of a certain concentration, and baked to dryness (lanthanum nitrate, analytical pure, Tianjin Kermel Chemical Reagent Co.,Ltd., phosphoric acid, 85%, The Chemical Reagent factory of Shenyang). The resulting material was catalyst A. The contents of ZSM-5, P and La in the catalyst were 85 wt %, 2.10 wt % and 1.05 wt %, respectively. * This Example does not fall within the scope of the present invention [0041] The reactions were carried out in a micro fixed bed reaction device under the following reaction conditions: the charge of catalyst A was 3g; the reaction temperature was 550°C; the feedstock was an 80 wt % aqueous methanol; the weight hourly space velocity (WHSV) of methanol was 1.5hr"1; and the reaction pressure was 0.1MPa. The resulting product was analyzed by a Varian CP-3800 Gas Chromatograph (Plot Capillary Column, programmed heating from 50°C to 200°C, FID).
[0042] The results of the reaction were shown in Table 1. As shown, the selectivities of ethylene, propylene and butylenes were 23-26 wt%, 33-35 wt% and 19-20 wt%, respectively. The ethylene/propylene ratio was 0.6-0.8 (weight ratio).
Table 1 Results of Reactions in Example 1
Example 2*: The conversion of methanol over a molecular sieve catalyst [0043] Catalyst B was prepared as follows: SAPO-34 (provided by Dalian Institute of Chemical Physics) was mixed well with clay, aluminum sol and silicasol (all commercially available from Zhejiang Yuda Chemical Industry CO., Ltd.), and dispersed in water to form a slurry. After shaping by spraying, microspheres with diameter of 20-100 pm were formed. The microspheres were baked at 600°C for 4 hours, and the resultant was catalyst B. The content of SAPO-34 in the catalyst was 30 wt %.
Table 2 Results of Reactions in Example 2
* This Example does not fall within the scope of the present invention [0044] The reactions were carried out in a pilot fluidized bed reaction device under the reaction conditions as follows: the total charge of catalyst B was 5Kg and the charge for the reactor bed was 1,25Kg; the recycle rate of the catalyst was 0.4-1 Kg/hr; the reaction temperature was 450-500°C; the feed was an 80 wt% aqueous methanol solution; the WHSV was 1.8hr'1, and the reaction pressure was 0.1 MPa. The reaction product was analyzed by a Varian CP-3800 Gas Chromatography with a Plot Column and a FID.
[0045] The results of the reactions were shown in Table 2. As shown, the selectivities of ethylene and propylene were 42-49 wt% and 32-39 wt%, respectively. The total selectivity of ethylene and propylene was 80-82 wt%. The ratio of ethylene/propylene was 1.0-1.5 by weight.
Example 3*: The reactions of co-feeding of ethylene and methanol over a molecular sieve catalyst [0046] Catalyst C was prepared as follows: after mixed with silicasol homogeneously, SAPO-34 (the raw materials and their sources are same as those in Examples 1 and 2) was shaped by mixing, kneading and extruding; air dried at room temperature; and baked at 550°C for 4 hours. The resultant was catalyst C. * This Example does not fall within the scope of the present invention [0047] The reactions were carried out in a micro fixed bed reaction device under the following reaction conditions: the charge of catalyst C was 1g; the reaction temperature was 450°C; the feedstock was a mixture of methanol and ethylene with the methanol content (C mol %) of 6-30%; the reaction contacting time was 1s; and the reaction pressure was 0.1 MPa. The resulting product was analyzed by a Varian CP-3800 Gas Chromatography with a Plot Column and a FID. The sampling time was 6 min.
[0048] The results of the reactions were shown in Table 3. As shown, the yield of C 3t% calculated on the basis of MeOH reached 90 wt % or higher.
Table 3 Results of Reactions in Example 3
Example 4*: The reactions of the co-feeding of ethylene-containing gas mixture and methanol over a molecular sieve catalyst [0049] Catalyst D was prepared as follows: after immersing in a magnesium nitrate solution and being dried off, a ZSM-5 molecular sieve was baked at 550°C. The resulting sample was mixed with clay, aluminum sol and silicasol, and dispersed in water to form a slurry. After shaping by spraying, microspheres with a diameter of 20-100 pm were formed (the raw materials and their sources are same as those in Examples 1 and 2). The microspheres were baked at 550°C for 4 hours, and the resultant was catalyst D. The contents of ZSM-5 and Mg in the catalyst were 30 wt % and 0.5 wt %, respectively. The reactions were carried out in a micro fluidized bed reaction device. The charge of the catalyst was 10g; the reaction temperature was 425°C; the liquid feedstock was an aqueous 30 wt % methanol solution; and the WHSV of methanol was 2.0hr'1, The gaseous feedstock was ethylene-containing gas mixture with the detailed composition shown in Table 4. The feeding ratio of ethylene/methanol was 3.5, and the reaction pressure was 0.1 MPa. The resulting product was analyzed by a Varian CP-3800 Gas Chromatography with a Plot Column and a FID. * This Example does not fall within the scope of the present invention [0050] The results of the reactions were shown in Table 5. As shown, conversion of methanol was 95-97%, and the yield of propylene calculated on the basis of methanol was 83 wt %.
Table 4 Composition Analysis of Ethylene-Containing Gas Mixture
Table 5 Results of Reactions in Example 4
Example 5*: The reactions of the co-feeding of butylene and methanol over a molecular sieve catalyst [0051] The catalyst used was same as that in Example 2. The reactions were carried out in a micro fixed bed reaction device under the following reaction conditions: the charge of catalyst C was 1g; the reaction temperature was 450°C; the feed was a mixture of methanol and butylenes-2 with the butylenes/methanol ratio of 5.24 (weight ratio); the WHSV based on methanol was 2.0hr"1, and the reaction pressure was 0.1 MPa. The reaction product was analyzed by a Varian CP-3800 Gas Chromatography with a Plot Column and a FID.
Table 6 Results of Reactions in Example 5
* This example does not fall within the scope of the present invention.
Example 6: [0052] The reaction flow in Figure 1 was utilized. Fluidized bed reactors were used in each reaction zone, and the reaction conditions such as catalysts, reaction temperature, pressure and WFISV, were shown in Table 7.
Table 7 Reaction Conditions of Each Reaction Zone in Example 6
Table 8 Composition of Each Stream in Example 6
[0053] The total feeding amount of methanol was 288 ton/hr, and the methanol feed was divided into 3 streams, i.e. stream 8, stream 9 and stream 10, with the proportions of 79.2 wt%, 16.3 wt% and 4.5 wt%, respectively. Methanol stream 8 (the flowrate of methanol was 228 ton/hr) entered into the reaction zone 1 and was transformed into the mixed stream 11 (with a flow rate of 98 ton/hr), including ethylene, propylene, butylenes and hydrocarbons with more carbon atoms. The stream 11 then entered into the separation zone 4 to undergo a preliminary separation. The streams 12 and 13 flowing out of the reaction zone 2 and 3, respectively, entered into the separation zone 4 as well. Three effluent streams, i.e., the materials containing ethylene, ethane and lighter fractions; the materials containing propylene and propane; and the materials containing C4 and heavier fractions, respectively, were formed in the separation zone 4. Among them, the stream 16 (with a flow rate of 86.1 ton/hr) containing propylene and propane underwent a separation step in the separation zone 5, so that propane was removed and the propylene product was generated. A portion of the material containing ethylene, ethane and lighter products (stream 14, with a flow rate of 118 ton/hr) entered the reaction zone 2, with the rest (stream 17, with a flowrate of 27.5ton/hr) entering the separation zone 6 to remove fractions other than ethylene. At least a portion of the material containing C4 and heavier fractions (stream 15, with a flow rate of 66 ton/hr) entered into the reaction zone 3, with the rest part (stream 18, 10.2 ton/hr) forming hydrocarbon products with 4 or more carbon atoms, or entering the separation zone 7 to form C4 product and product with 5 or more carbon atoms. The stream 12 (with a flow rate of 138.3 ton/hr) flowing out of the reaction zone 2 and containing propylene, and the stream 13 (with a flow rate of 71.5 ton/hr) flowing out of the reaction zone 3 and containing ethylene, propylene and hydrocarbons with 4 and more carbon atoms, entered into the separation zone 4.
[0054] The flow rates and compositions of each stream in the flow chart were shown in details in Table 8. Calculated on the basis of total flow rate of the methanol feed and the composition of stream 16, 17 and 18, the selectivity of propylene obtained by the technical process described above was 66.5 wt%. The total selectivity of ethylene and propylene was 85 wt %. The ratio of ethylene/propylene was 0.28 (weight ratio).
Example 7: [0055] The reaction flow, the type of reactors and catalysts in each reaction zone were as same as those in Example 6. The reaction conditions, such as temperature, pressure and WHSV.were shown in Table 9.
Table 9 Reaction Conditions of Each Reaction Zone in Example 7
Table 10 Composition of Each Stream in Example 7
[0056] The total feeding flow rate of methanol was 318 ton/hr, and the methanol feedstock was divided into 3 streams, i.e. stream 8, stream 9 and stream 10, with the proportions of 71.7 wt%22.2 wt%and 6.1wt%, respectively. The flowrate and composition of each stream in the flow chart were shown in details in Table 10. Calculated on the basis of the total flow rate of the feedstock, i.e. methanol, and the composition of stream 16, 17 and 18, the selectivity of propylene obtained by the technical process described above was 76.4 wt%. The total selectivity of ethylene and propylene was 87.6 wt%. The ratio of ethylene/propylene was 0.15 (weight ratio).
Example 8: [0057] The reaction flow, the type of reactors and catalysts in each reaction zone were as same as those in Example 7. The reaction conditions, such as temperature, pressure and WHVS, were shown in Table 11.
Table 11 Reaction Conditions of Each Reaction Zone in Example 7
Table 12 Composition of Each Stream in Example 8
[0058] The total feeding flow rate of dimethyl ether was 228.6 ton/hr, and the dimethyl ether feedstock was divided into 3 streams, i.e. stream 8, stream 9 and stream 10, with the proportions of 71.7 wt% 22.2 wt% and 6.1 wt%, respectively. The flow rate and composition of each stream in the flowchart were shown in details in Table 12. calculated on the basis of total flow of the feedstock, i.e. dimethyl ether, and the composition of stream 16, 17 and 18, the selectivity of propylene obtained by the technical method described above was 76.4 wt%. The total selectivity of ethylene and propylene was 87.6 wt %. The ratio of ethylene/propylene was 0.15 (weight ratio).
REFERENCES CITED IN THE DESCRIPTION
This list of references cited by the applicant is for the reader's convenience only. It does not form part of the European patent document. Even though great care has been taken in compiling the references, errors or omissions cannot be excluded and the EPO disclaims all liability in this regard.
Patent documents cited in the description • USS6139S131 (00031 • CISI1352627A [00031 • CN'i 302283.A f000-f· • US650695431 [00041 • US653816731 f00041 • US6710218B1 [00051 • US643720831. [0006] • 118874079082 Γ00061 • US845574781 ΓΟΟΟΤ] • US655224Q31 [0807] . US671702382 l'OOOVl • CN1163458C [0008] • US661395031 [OSOS] • US-374374731 [00101 • USe051748A1 fOOUl . USS51847532 [00121 • US20050215640.A1 [0013] • US6965Q5782 [0013] • USe-37397882 [00141 • .QN1356299A £0015] . CN1190395C ΓΟΟΙβΙ • CN1.197835C [0017] • US644126231 [0018] • CN1489563A [00181 • CA2408590 [0018] . US5914438A 100181 • US830383981 [00181 • US5990369A [0019] • W02005056504A1 [0024]
Non-patent literature cited in the description • Kinetic studies of zeolite-catalyzed methylation reactionsJ. Catal., 2004, vol. 224, 1115-123 [0021]
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PCT/CN2007/002267 WO2008106841A1 (en) | 2007-03-07 | 2007-07-27 | A process for producing lower carbon olefins from methanol or/and dimethyl ether |
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Families Citing this family (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102060644B (en) * | 2009-11-17 | 2013-07-10 | 中国石油化工集团公司 | Method for preparing olefin by dehydration of methanol |
CN102060645B (en) * | 2009-11-17 | 2013-07-24 | 中国石油化工集团公司 | Process for preparing olefins by methanol dehydration |
CN101973830A (en) * | 2010-09-03 | 2011-02-16 | 江苏煤化工程研究设计院有限公司 | Technology for preparing olefin and co-producing alcohol ether fuel environment-friendly additive by using dimethyl ether |
CN102464530B (en) * | 2010-11-17 | 2014-04-23 | 中国石油化工股份有限公司 | Method for catalytically converting methanol into low-carbon olefins |
CN102531821B (en) | 2010-12-28 | 2015-03-25 | 中国科学院大连化学物理研究所 | Method for catalyzing catalytic cracking reaction of methanol coupled with naphtha using modified ZSM-5 molecular sieve based catalyst |
SG11201400355TA (en) * | 2011-09-07 | 2014-04-28 | Shell Int Research | Process for preparing ethylene and propylene from a feedstock comprising a tert - alkyl ether |
DE102012215757A1 (en) * | 2012-09-05 | 2014-03-06 | Evonik Industries Ag | Process for the preparation of linear butenes from methanol |
CN103739425B (en) * | 2012-10-17 | 2015-09-09 | 中国石油化工股份有限公司 | For improving the reaction unit of ethene, propene yield in methanol-to-olefins reaction process |
WO2014102290A1 (en) | 2012-12-28 | 2014-07-03 | Shell Internationale Research Maatschappij B.V. | Process for the preparation of an olefinic product from an oxygenate |
WO2018096171A1 (en) | 2016-11-28 | 2018-05-31 | Basf Se | Catalyst composite comprising an alkaline earth metal containing cha zeolite and use thereof in a process for the conversion of oxygenates to olefins |
CN106631676B (en) * | 2016-12-09 | 2019-10-22 | 中国科学院大连化学物理研究所 | Alkylation of toluene prepares the moving bed process of paraxylene co-producing light olefins |
CN109647503B (en) * | 2017-10-10 | 2021-11-16 | 中国石油化工股份有限公司 | Composite catalyst for preparing low-carbon olefin from synthesis gas, preparation method thereof and method for preparing low-carbon olefin from synthesis gas |
CN109374804B (en) * | 2018-10-31 | 2020-11-03 | 内蒙古中煤蒙大新能源化工有限公司 | Chromatographic analysis method for propane product in methanol-to-olefin process production |
CN116375551B (en) * | 2023-04-14 | 2024-03-29 | 浙江大学 | Method for preparing ethylene from alkoxy benzene with high selectivity |
Family Cites Families (34)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3906054A (en) | 1974-09-23 | 1975-09-16 | Mobil Oil Corp | Alkylation of olefins |
AU700339B2 (en) | 1995-01-18 | 1998-12-24 | Owens-Brockway Glass Container Inc. | Method and apparatus for delivering a coated glass stream for forming charges of glass |
US5990369A (en) * | 1995-08-10 | 1999-11-23 | Uop Llc | Process for producing light olefins |
US6538167B1 (en) | 1996-10-02 | 2003-03-25 | Exxonmobil Chemical Patents Inc. | Process for producing light olefins |
US6046372A (en) | 1996-10-02 | 2000-04-04 | Mobil Oil Corporation | Process for producing light olefins |
US6051746A (en) | 1997-06-18 | 2000-04-18 | Exxon Chemical Patents Inc. | Oxygenate conversions using modified small pore molecular sieve catalysts |
US6455747B1 (en) | 1998-05-21 | 2002-09-24 | Exxonmobil Chemical Patents Inc. | Method for converting oxygenates to olefins |
US6552240B1 (en) | 1997-07-03 | 2003-04-22 | Exxonmobil Chemical Patents Inc. | Method for converting oxygenates to olefins |
ATE256648T1 (en) * | 1997-09-24 | 2004-01-15 | Dijk Technology L L C Van | FIXED BED PROCESS FOR CONVERSION OF METHANOL USING A SILICO-ALUMINUM OXIDE-PHOSPHATE MOLECULAR SIEVE AS A CATALYST |
RO114524B1 (en) | 1997-10-02 | 1999-05-28 | Sc Zecasin Sa | Process for producing olefins with low molecular mass by fluidized bed catalytic conversion of methanol |
US6455749B1 (en) * | 1997-10-03 | 2002-09-24 | Exxonmobil Chemical Patents, Inc. | Method for increasing light olefin yield by conversion of a heavy hydrocarbon fraction of a product to light olefins |
US6613951B1 (en) | 1999-09-23 | 2003-09-02 | Mobil Oil Corporation | Process for converting methanol to olefins |
US6437208B1 (en) | 1999-09-29 | 2002-08-20 | Exxonmobil Chemical Patents Inc. | Making an olefin product from an oxygenate |
US6531639B1 (en) | 2000-02-18 | 2003-03-11 | Exxonmobil Chemical Patents, Inc. | Catalytic production of olefins at high methanol partial pressures |
US7232936B1 (en) * | 2000-02-22 | 2007-06-19 | Exxonmobil Chemical Patents Inc. | Conversion of oxygenate to olefins with staged injection of oxygenate |
US6743747B1 (en) | 2000-02-24 | 2004-06-01 | Exxonmobil Chemical Patents Inc. | Catalyst pretreatment in an oxgenate to olefins reaction system |
US6506954B1 (en) | 2000-04-11 | 2003-01-14 | Exxon Mobil Chemical Patents, Inc. | Process for producing chemicals from oxygenate |
DE10117248A1 (en) * | 2000-05-31 | 2002-10-10 | Mg Technologies Ag | Process for producing propylene from methanol |
US6613950B1 (en) | 2000-06-06 | 2003-09-02 | Exxonmobil Chemical Patents Inc. | Stripping hydrocarbon in an oxygenate conversion process |
US6303839B1 (en) * | 2000-06-14 | 2001-10-16 | Uop Llc | Process for producing polymer grade olefins |
US6441262B1 (en) | 2001-02-16 | 2002-08-27 | Exxonmobil Chemical Patents, Inc. | Method for converting an oxygenate feed to an olefin product |
US6518475B2 (en) | 2001-02-16 | 2003-02-11 | Exxonmobil Chemical Patents Inc. | Process for making ethylene and propylene |
US6673978B2 (en) | 2001-05-11 | 2004-01-06 | Exxonmobil Chemical Patents Inc. | Process for making olefins |
US6780218B2 (en) | 2001-06-20 | 2004-08-24 | Showa Denko Kabushiki Kaisha | Production process for niobium powder |
CN1156416C (en) | 2001-12-14 | 2004-07-07 | 清华大学 | Process and system for preparing low-carbon olefin from methanol or dimethylether |
US20040064007A1 (en) * | 2002-09-30 | 2004-04-01 | Beech James H. | Method and system for regenerating catalyst from a plurality of hydrocarbon conversion apparatuses |
EP1508555A1 (en) * | 2003-08-19 | 2005-02-23 | Total Petrochemicals Research Feluy | Production of olefins |
US7214636B2 (en) * | 2003-08-22 | 2007-05-08 | Exxonmobil Chemical Patents Inc. | Catalyst regenerator for reducing entrained catalyst loss |
JP4608926B2 (en) * | 2004-03-30 | 2011-01-12 | 三菱化学株式会社 | Propylene production method |
KR101159087B1 (en) | 2003-12-12 | 2012-06-25 | 미쓰비시 가가꾸 가부시키가이샤 | Process for producing propylene |
CN100494129C (en) * | 2003-12-12 | 2009-06-03 | 三菱化学株式会社 | Method for producing propylene |
US6965057B2 (en) | 2004-03-24 | 2005-11-15 | Exxonmobil Chemical Patents Inc. | Oxygenate to olefin process |
US7371915B1 (en) * | 2004-06-25 | 2008-05-13 | Uop Llc | Conversion of oxygenate to propylene using moving bed technology |
US20100022815A1 (en) * | 2005-08-24 | 2010-01-28 | Jgc Corporation | Process for production of lower hydrocarbons and apparatus for the production |
-
2007
- 2007-03-07 CN CN2007100642323A patent/CN101157593B/en active Active
- 2007-07-27 JP JP2009552045A patent/JP5313929B2/en active Active
- 2007-07-27 US US12/529,912 patent/US8148587B2/en active Active
- 2007-07-27 DK DK07785182.2T patent/DK2133319T3/en active
- 2007-07-27 EP EP07785182.2A patent/EP2133319B1/en active Active
- 2007-07-27 BR BRPI0721456A patent/BRPI0721456B1/en not_active IP Right Cessation
- 2007-07-27 AU AU2007348551A patent/AU2007348551B2/en active Active
- 2007-07-27 KR KR1020097020761A patent/KR101138849B1/en active IP Right Grant
- 2007-07-27 WO PCT/CN2007/002267 patent/WO2008106841A1/en active Application Filing
- 2007-07-27 MY MYPI20093426 patent/MY152862A/en unknown
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KR101138849B1 (en) | 2012-05-15 |
WO2008106841A1 (en) | 2008-09-12 |
BRPI0721456A2 (en) | 2014-07-22 |
EP2133319B1 (en) | 2016-06-15 |
AU2007348551A1 (en) | 2008-09-12 |
JP5313929B2 (en) | 2013-10-09 |
WO2008106841A8 (en) | 2009-10-01 |
EP2133319A1 (en) | 2009-12-16 |
AU2007348551B2 (en) | 2010-11-25 |
BRPI0721456B1 (en) | 2017-01-17 |
US8148587B2 (en) | 2012-04-03 |
CN101157593B (en) | 2010-09-22 |
US20100063336A1 (en) | 2010-03-11 |
MY152862A (en) | 2014-11-28 |
KR20090118995A (en) | 2009-11-18 |
CN101157593A (en) | 2008-04-09 |
JP2010520239A (en) | 2010-06-10 |
ZA200906774B (en) | 2010-12-29 |
EP2133319A4 (en) | 2013-08-14 |
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